Synthetic polymer compositions containing charge transfer complexes, their preparation and the use thereof

ABSTRACT

A composition comprising a) a thermosetting, thermoplastic or structurally crosslinked polymer and b) a charge transfer complex of formula I in the form of a network of crystal needles in the polymer matrix 
     
         [A].sup.⊖ B.sup.⊕                              (I), 
    
     wherein A is a compound of formula II or a mixture of compounds of formula II ##STR1## wherein the R substituents are identical and are H or C 1  -C 4  alkyl, or the adjacent R substituents, taken together, are --(CH 2 ) 3  --or --(CH 2 ) 4  --; R 1  or C 1  -C 4  alkyl; and H 1  is ═N--CN, and X 2 , X 3  and X 4  are each independently of one another ═O or ═N--CN, and B is a compound of formula III or IIIa ##STR2## wherein R 2 , R 3 , R 4  and R 5  are each independently of one another H, linear or branched C 1  -C 18  -alkyl-(Z 1 ) n  --, phenyl-(Z 1 ) n  - or benzyl-(Z 1 ) n  --which are unsubstituted or substituted by C 1  -C 4  alkyl, C 1  -C 4  alkyl, C 1  -C 4  alkoxy or C 1  -C 4  alkylthio, or R 2  and R 3  as well as R 4  and R 5  are together, each independently of the other, trimethylene, tetramethylene, --Z 2  --(CH 2 )--Z 2  --, --Z 2  --(CH 2 ) 2  --Z 2  --, --Z 1  --CH═CH--Z 1  --or --CH═CH--CH═CH--, each unsubstituted or substituted by C 1  -C 4  alkyl, C 1  -C 4  alkoxy or C 1  -C 4  alkylthio, n is 0 or 1 steht, Y 1  and Y 2  are each independently of the other --S--or --Se--, Z 1  is --S-- or --Se--, Z 2  is --O--, --S--or --Se--, Z is --S--, --Se--or NR 7 , and R 7  is H, C 1  -C 6  alkyl, phenyl or benzyl, and R 6  is H, C 1  -C 4  alkyl, phenyl or benzyl. The composition is an electric conductor.

SYNTHETIC POLYMER COMPOSITIONS CONTAINING CHARGE TRANSFER COMPLEXES,THEIR PREPARATION AND THE USE THEREOF

The present invention relates to compositions comprising a syntheticpolymer and a charge transfer complex (hereinafter abbreviated to CTcomplex) of pentacenecyanoiminc derivatives as electron acceptors andchalcogenated fulvalenes as electron donors; to a process for theirpreparation; and to the use of said compositions as electric conductors,conveniently for making electrically conductive films, foils orcoatings. These CT complexes are radical cation salts.

Powdered CT complexes comprising tetra-substituted pentacenecyanoimineand tetrathiofulvalene as electron donors and having a conductivity ofabout 6 S/cm are described in Synthetic Metals, 41-43, pages 2365-2375(1991). However, powdered materials are insufficiently able to enhancethe conductivity of polymer materials, as after processing the particlesare encapsulated by the polymer material and therefore insulated.

U.S. Pat. No. 5,009,812 discloses antistatically treated and conductivepolymers that contain e.g. CT complexes of tetrathio-, tetraseleno- ortetratellurotetracenes as electron donors and halogens or oxygen aselectron accepton. In these materials the CT complexes form needlenetworks in the polymer matrix. The preparation of these conductivepolymers necessitates the use of reagents that cause corrosion inmetallic machine pans, so that special measures have to be taken toprotect the machines. In addition, the poor solubility of chalcogenictetracenes makes rather high temperatures necessary for the preparationof the polymers. This is regarded as uneconomic and also requiresindustrial hygiene measures owing to the too high volatility of thereagants used. In addition, the use of tetraseleno- andtetratellurotetracenes is considered questionable for toxicologicalreasons.

Surprisingly, it has been found that pentacenecyanoimines and specificfulvalene derivatives form CT complexes which, unexpectedly, even in thepresence of binders, crystallise in needle form, have a highconductivity and exert virtually no corrosive action on the metallicpans of processing machines. The starting compounds are also soluble inless polar organic solvents so that no very high temperatures arerequired for the preparation of the CT complexes. The CT complexes havesuperior stability to moisture and heat.

In one of its aspects, the invention relates to a composition comprisinga) a thermosetting, thermoplastic or structurally crosslinked polymerand b) a charge transfer complex of formula I in the form of a networkof crystal needles in the polymer matrix

    [A].sup.⊖ ·B.sup.⊕                    (I),

wherein A is a compound of formula II or a mixture of compounds offormula II ##STR3## wherein the R substituents are identical and are Hor C₁ -C₄ alkyl, or the adjacent R substituents, taken together, are--(CH₂)₃ --or --(CH₂)₄ ; R₁ is H or C₁ -C₄ alkyl; and X₁ is ═N--CN, andX₂, X₃ and X₄ are each independently of one another ═O or ═N--CN, and Bis a compound of formula III or IIIa ##STR4## wherein R₂, R₃, R₄, and R₅are each independently of one another H, linear or branched C₁ -C₁₈alkyl-(Z₁)_(n) --, phenyl-(Z₁)_(n) --or benzyl-(Z₁)_(n) which areunsubstituted or substituted by C₁ -C₄ alkyl, C₁ -C₄ alkoxy or C₁ -C₄alkylthio, or R₂ and R₃ as well as R₄ and R₅ are together, eachindependently of the other, trimethylene, tetramethylene, --Z₂--(CH₂)--Z₂ --, --Z₂ --(CH₂)₂ --Z₂ --, --Z₁ --CH═CH--Z₁ --or--CH═CH--CH═CH--, each unsubstituted or substituted by C₁ -C₄ alkyl, C₁-C₄ alkylthio, n is 0 or 1 steht, Y₁ and Y₂ are each independently ofthe other --S--or --Se--, Z₁ is --S--or --Se--, Z₂ is --O--, --S--or--Se--, Z is --S--, --Se--or NR₇, and R₇ is H, C₁ -C₆ alkyl, phenyl orbenzyl, and R₆ is H, C₁ -C₄ alkyl, phenyl or benzyl.

R and R₁ defined as alkyl may be methyl, ethyl, n- or isopropyl or n-,iso- or tert-butyl. Preferred alkyl radicals are methyl and ethyl. In apreferred embodiment of the invention, the R substituents are C₁ -C₄alkyl and the R₁ substituents are H, or the R₁ substituents are C₁ -C₄alkyl and the R substituents are H. Preferably R and R₁ are H, methyl orethyl. In a particularly preferred embodiment of the invention, R and R₁are H.

In another preferred embodiment of the invention, X₁ and X₄ are ═N--CNand X₂ and X₃ are ═O or ═N--CN, or X₂ and X₃ are ═N--CN and X₁ and X₄are ═O or ═N--CN. The most preferred meaning of X₁, X₂, X₃, and X₄ is═N--CN.

The compound of formula II is preferably5,7,12,14-pentacenetetracyanoimine which is in pure form or contains upto 10 % by weight, based on the total composition, of compounds offormula II in which one or two cyanoimine groups are replaced by oxygen.

The compounds of formulae III and IIIa preferably have a reductionpotential of less than or equal to 0.44 V, based on the standard calomelelectrode.

In the compounds of formula III, R₂ and R₃ and R₄ and R₅ are preferablyidentical and, most preferably, R₂ to R₅ are identical.

In a preferred embodiment of the invention, Y₁ and Y₂ in the compoundsof formulae III and IIIa are either --S--or --Se--, and, mostpreferably, --S--.

R₂ to R₅ defined as alkyl-(Z₁)_(n) --are preferably C₁ -C₁₂-alkyl-(Z₁)_(n) --, more particularly C₁ -C₈ alkyl-(Z₁)-_(n), moreparticularly C₁ -C₈ alkyl-(Z₁)-_(n) and, most preferably, C₁ -C₄alkyl-(Z₁)-_(n). Alkyl is preferably linear alkyl. Exemplary alkylgroups are methyl, ethyl, n- and isopropyl, n-, iso- and tert-butyl,pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl,tetradecyl, hexadecyl and octadecyl.

Methyl, ethyl, n- and isopropyl, n-, iso- and tert-butyl are especiallypreferred.

In a preferred embodiment of the invention, the group alkyl--(Z₁)_(n)--is methyl, ethyl, n- and isopropyl, n-, iso- and tert-butyl,methylthio, methylseleno, ethylthio and ethylseleno.

The C₁ -C₄ alkyl, C₁ -C₄ alkoxy and C₁ -C₄ alkylthio substituents maytypically be methyl, ethyl, n- and isopropyl, n-, iso- and tert-butyl aswell as corresponding alkoxy and alkylthio radicals. Preferredsubstituents are methyl, ethyl, n- and isopropyl, n- and isobutyl,methoxy, ethoxy, methylthio and ethylthio.

Typical examples of the phenyl--(Z₁)_(n) --or benzyl--(Z₁)_(n) --groupsare phenyl, benzyl, phenylthio, phenylseleno, benzylthio, benzylseleno,methylphenyl, methylbenzyl, ethylphenyl, n- or isopropylphenyl, n-, iso-or tert-butylphenyl, dimethylphenyl, dimethylbenzyl, methoxyphenyl,methylthiophenyl, methylthiobenzyl, methylphenylthio andmethylphenylseleno.

In formula IIIa R₆ is preferably H or C₁ -C₄ alkyl. The most preferredmeaning of R₆ is H, methyl or ethyl.

Z in formula IIIa is preferably --S--or --NR₇ --and, most preferably,--NR₇ --. R₇ is preferably H or C₁ -C₄ alkyl, and is most preferably H,methyl or ethyl.

Z₁ is preferably --S--and Z₂ is preferably --O--or --S--.

A preferred subgroup of the compounds of formula I comprises thosecompounds wherein in formula II R is H, methyl or ethyl and is mostpreferably H, R₁ is H or methyl and most preferably H, and X₁ to X₄ is═N--CN, and, in formulae 1II and IIIa, R₂ and R₃ as well as R₄ and R₅ orR2 to R₅ are identical and are H, linear or branched C₁ -C₈ alkyl--(Z₁)_(n) --, unsubstituted or C₁ -C₄ alkyl-substituted phenyl--(Z₁)_(n) --orbenzyl--(Z₁)_(n) --, or R₂ and R₃ and R₄ and R₅ are each togetherindependently of the other unsubstituted or C₁ -C₄ alkyl-substitutedtrimethylene, tetramethylene, --Z₂ --(CH₂)--Z₂ --, --Z₂ --(CH₂)--/Z₂ --,--Z₂ --(CH₂)₂ --Z₂ --, --Z₁ --CH═ CH--Z₁ --or --CH═CH--CH═CH--, n is 0or 1, Y₁ and Y₂ are --S--, Z₁ is --S--, Z₂ is --O--or --S--, Z is--S--or NR₇, and R₇ is H or C₁ -C₄ alkyl, and R₆ is H or C₁ -C₄ alkyl.

A particularly preferred subgroup of the compounds of formula Icomprises those compounds wherein, in formula II, R and R₁ are H, X₁ toX₄ are ═N--CN, and in formulae III and IIIa R₂ to R₅ are identical andare H, or are linear or branched C₁ -C₄ alkyl--(Z₁)_(n) --, or R₂ and R₃as well as R₄ and R₅ are each together trimethylene, tetramethylene,--Z₂ --(CH₂)--Z₂ --, --Z₂ --(CH₂)₂ --Z₂ --, --Z₁ --CH═CH--Z₁ or--CH═CH--CH═CH--, n is 0 or 1, Y₁ and Y₂ are --S--, Z₁ is --S--, Z₂--O--or --S--, Z is --S--or NR₇, and R₇ is H or C₁ -C₄ alkyl, and R₆ isH or C₁ -C₄ alkyl.

In a particularly preferred embodiment of the invention, the novelcompositions contain those compounds of formula I, wherein A is5,7,12,14-pentacenetetracyanoimine and B is a compound of formula IIIb##STR5## wherein Y₁ and Y₂ are each --S--, and R₂, R₃, R₄ and R₅ areeach independently of one another H, C₁ -C₄ alkyl or C₁ -C₄ alkylthio orR₂ and R₃ as well as R₄ and R₅ when taken together, are each --S--CH₂CH₂ --S--. Preferably R₂ and R₃ and R₄ and R₅ in formula IIIb areidentical radicals and, most preferably, R₂ to R₅ are identicalradicals.

Illustrative examples of CT complexes of formula I are those wherein Ain formula I is 5,7,12, 14-pentacenetetracyanoimine, and B istetrathiofulvalene, tetramethyltetrathiofulvalene,tetramethyltetrathiofulvalene, dimethyldiethyltetrathiofulvalene,tetra-n-propyltetrathiofulvalene, tetra-n-butyltetrathiofulvalene,tetra(methylthio)tetrathiofulvalene, tetra(ethylthio)tetrathiofulvalene,tetra(n-propylthio)tetrathiofulvalene,tetra(n-butylthio)tetrathiofulvalene,dimethyldimethylthiotetrathiofulvalene,diethyldimethylthiotetrathiofulvalene,diethylthiodimethylthiotetrathiofulvalene and tetraselenofulvalene.

In another of its aspects, the invention relates to a process for thepreparation of CT complexes of formula I, which comprises reactingequimolar amounts of a fulvalene derivative B and a pentacenecyanoimineof formula II in an inert organic solvent. Equimolar amounts means thatabout 1 equivalent of the fulvalene derivative of formula III or IIIa isreacted with about 1 equivalent of the pentacenecyanoimine of formula IIto form the 1:1 complexes.

The fulvalene derivatives are known, some are commercially available orthey can be prepared by known standard methods. The preparation of5,7,12,14-pentacenetetracyanoimine is described by L. L. Miller inSynthetic Metals, 41-43, pages 2365-2375 (1991). The startingunsubstituted or substituted 5,7,12,14-pentacenetetrones are obtainableby a process described by W. H. Mills et. al. in J. Chem. Soc. 101, page2194 (1912). The 5,7,12,14-pentacenetetracyanoimines can be purified byconventional methods, conveniently by recrystallization orchromatographic methods. If no special protective measures are taken,for example anhydrous conditions, cyanoimine groups can be replaced byoxygen, but without adversely affecting the formation of the desired CTcomplexes.

The inventive process is conveniently carded out at elevatedtemperature, typically at 30°-200° C., preferably at 50°-100° C.

Suitable solvents are typically non-polar, polar and aprotic solventswhich may be used singly or in mixtures of at least two solvents.Typical examples are: ethers (dibutyl ether, tetrahydrofuran, dioxane,ethylene glycol monomethyl or dimethyl ether, ethylene glycol monoethylor diethyl ether, diethylene glycol diethyl ether, triethylene glycoldimethyl ether), halogenated hydrocarbons (methylene chloride,chloroform, 1,2-dichlorethane, 1,1,1-trichloroethane,1,1,2,2-tetrachloroethane), carboxylates and lactones (ethyl acetate,methyl propionate, ethyl benzoate, 2-methoxyethylacetate,γ-butyrolactone, δ-valerolactone, pivalolactone), carboxamides andlactams (N,N-dimethylformamide, N,N-diethylformamide,N,N-dimethylacetamide, tetramethylurea, hexamethylphosphoric triamide,γ-butyrolactam, ε-caprolactam, N-methylpyrrolidone, N-acetylpyrrolidone,N-methylcaprolactam), sulfoxides (dimethyl sulfoxide), sulfones(dimethyl sulfone, diethyl sulfone, timethylene sulfone, tetramethylenesulfone), tertiary amines (N-methylpiperidine, N-methylmorpholine),substituted benzenes (benzonitrile, chlorobenzene, o-dichlorobenzene,1,2,4-trichlorobenzene, nitrobenzene, toluene, xylene), nitriles(acetoniuile, propionitrile) and aliphatic or cycloaliphatichydrocarbons (petroleum ether, pentane, hexane, cyclohexane andmethylcyclohexane). Suitable solvents are also aromatic-aliphaticethers, for example methyl or ethyl phenyl ether, and ketones such asacetone, methyl ethyl ketone, methyl propyl ketone, dipropyl ketone,dibutyl ketone and methyl isobutyl ketone.

The CT complexes obtainable by the process of this invention areobtained in great purity and, after filtration, need only be washed withsolvents. Ordinarily they are obtained as dark coloured to blackneedle-shaped crystals which have conductivities of more than 0.1 S/cm.They therefore have excellent suitability for use as electricconductors. Depending on the type of CT complex and on the amount addedit is possible to obtain electrically conductive or antistaticallytreated polymers by incorporating these CT complexes in polymermaterials, the CT complex being present in the polymer matrix as anetwork of crystal needles. Depending on the concentration of CT complexin the polymer matrix, very fine meshed needle networks can be obtained.

In yet another of its aspects, the invention relates to CT complexes offormula Ia

    [A].sup.⊖ ·B.sup.⊕                    (Ia),

wherein A is a compound of formula II or a mixture of compounds offormula II, ##STR6## wherein the R substituents are identical and are Hor C₁ -C₄ alkyl, or the adjacent R substituents, taken together, are--(CH₂)₃ --or--(CH₂)₄ --; R₁ is H or C₁ -C₄ alkyl; and X₁ is ═N--CN, andX₂, X₃ and X₄ are each independently of one another ═O or ═N--CN, and Bis a compound of formula III or IIIa ##STR7## wherein R₂, R₃, R₄ and R₅are each independently of one another H, linear or branched C₁ -C₁₈alkyl--(Z₁)_(n) --, phenyl--(Z₁)_(n) --or benzyl--(Z₁)_(n) --which areunsubstituted or substituted by C₁ -C₄ alkyl, C₁ -C₄ alkoxy or C₁ -C₄alkylthio, or R₂ and R₃ as well as R₄ and R₅ are each independently ofthe other trimethylene, tetramethylene, --Z₂ --(CH₂)--Z₂ --, --Z₂--(CH₂)₂ --Z₂ --, --Z₁ --CH═CH--Z₁ --or --CH═CH--CH═CH--, eachunsubstituted or substituted by C₁ -C₄ alkyl, C₁ -C₄ alkoxy or C₁ -C₄alkylthio, n is 0 or 1 steht, Y₁ and Y₂ are each independently of theother --S--or --Se--, Z₁ is --S-- or --Se--, Z₂ is --O--, --S--or--Se--, Z is --S--, --Se--or NR₇, and R₇ is H, C₁ -C₆ alkyl, phenyl orbenzyl, and R₆ is H, C₁ -C₄ alkyl, phenyl or benzyl, with the exceptionof [(5,7,12,14-tetracenetetracyanoimine)(tetrahiofulvalene)].

In yet another of its aspects, the invention relates to CT complexes offormula I with the exception of[(5,7,12,14-tetracenetetracyanoimine)(tetrathiofulvalene)] in the formof needle-shaped crystals.

In respect of the novel CT complexes of formula I, the same preferencesand exemplary embodiments apply as cited previously with respect to theCT complexes in the novel compositions.

The novel compositions may contain the CT complex in a concentration of0.01 to 30 % by weight, preferably of 0.01 to 20 % by weight, moreparticularly of 0.01 to 10 % by weight and, most preferably, of 0.1 to 5% by weight, based on said composition.

The thermoplastic polymers may conveniently be selected from among thefollowing polymers, copolymers or mixtures of these polymers:

1. Polymers of monoolefins and diolefins, for example polypropylene,polyisobutylene, polybut-1-ene, polymethylpent-1-ene, polyisoprene orpolybutadiene, as well as polymers of cycloolefins, for example ofcyclopentene or norbomene, polyethylene (which can be uncrosslinked orcrosslinked), for example high density polyethylene (HDPE), low densitypolyethylene (LDPE), linear low density polyethylene (LLDPE), branchedlow density polyethylene (BLDPE).

2. Mixtures of the polymers mentioned under 1 ), for example mixtures ofpolypropylene with polyisobutylene, polypropylene with polyethylene (forexample PP/HDPE, PP/LDPE) and mixtures of different types ofpolyethylene (for example LDPF/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, for example ethylene/propylene copolymers, linear lowdensity polyethylene (LLDPE) and mixtures thereof with low densitypolyethylene (LDPE), propylene/but-1-ene copolymers, ethylene/hexenecopolymers, ethylene/ethylpentene copolymers, ethylene/heptenecopolymers, ethylene/octene copolymers, propylene/isobutylenecopolymers, ethylene/but-1-ene copolymers, propylene/butadienecopolymers, isobutylene/isoprene copolymers, ethylene/alkyl acrylatecopolymers, ethylene/allcyl methacrylate copolymers, ethylene/vinylacetate or ethylene/acrylic acid copolymers and the salts thereof(ionomers), as well as terpolymers of ethylene with propylene and adiene, such as hexadiene, dicyclopentadiene or ethylidene-norbornene;and also mixtures of such polymers with one another and with polymersmentioned in 1 ) above, for example polypropylene/ethylene-propylenecopolymers, LDPE/ethylene-vinyl acetate copolymers (EVA),LDPE/ethylene-acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA andalternating or random polyalkylene/carbon monoxide copolymers andmixtures thereof with other polymers, for example polyamides.

3a. Hydrocarbon resins (for example C₅ -C₉)including hydrogenatedmodifications thereof (for example tackifiers) and mixtures ofpolyalkylenes and starch.

4. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

5. Copolymers of styrene or α-methylstyrene with dienes or acrylicderivatives, for example styrene/butadiene, styrene/acrylonitrile,styrene/alkyl methacrylate, styrene/maleic anhydride,styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylatestyrene/acrylonitrile/methyl acrylate; mixtures of high impact strengthfrom styrene copolymers and another polymer, for example from apolyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer;and block copolymers of styrene, for example styrene/butadiene/styrene,styrene/isoprene/styrene, styrene/ethylene/butylene/-styrene orstyrene/ethylene/propylene/styrene.

6. Graft copolymers of styrene or α-methylstyrene, for example styreneon polybutadiene, styrene on polybutadiene-styrene orpolybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (ormethacrylonitrile) on polybutadiene; styrene and maleic anhydride ormaleimide on polybutadiene; styrene, acrylonitrile and maleic anhydrideor maleimide on polybutadiene; styrene, acrylonitrile and methylmethacrylate on polybutadiene, styrene and alkyl acrylates ormethacrylates on polybutadiene, styrene and acrylonitrile onethylene/propylene/diene terpolymers, styrene and acrylonitrile onpolyacrylates or polymethacrylates, styrene and acrylonitrile onacrylate/butadiene copolymers, as well as mixtures thereof with thecopolymers listed in 5), for example the copolymer mixtures known asABS, MBS, ASA or AES polymers.

7. Halogen-containing polymers, such as polychloroprene, chlorinatedrubbers, chlorinated or chlorosulfonated polyethylene, copolymers ofethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers,polymers of halogenated vinyl compounds, for example polyvinyl chloride,polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, aswell as copolymers thereof, for example vinyl chloride/vinylidenechloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinylacetate copolymers.

8. Polymers derived from α,β-unsaturated acids and derivatives thereof,such as polyacrylates and polymethacrylates, polymethyl methacrylateimpact-modified with butyl acrylate, polyacrylamides andpolyacrylonitrile.

9. Copolymers of the monomers mentioned in 8) with each other or withother unsaturated monomers, for example acrylonitrile/butadiene,acrylonitrile/alkyl acrylate, acrylonitrile/alkoxyalkyl acrylate oracrylonitrile/vinyl halide copolymers or acrylonitrile/alkylmethacrylate/butadiene terpolymers.

10. Polymers derived from unsaturated alcohols and amines, or acylderivatives thereof or acetals thereof, such as polyvinyl alcohol,polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinylmaleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine;as well as their copolymers with olefins mentioned in 1 ) above.

11. Homopolymers and copolymers of cyclic ethers, such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bis(glycidyl) ethers.

12. Polyacetals such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as a comonomer, polyacetals modified withthermoplastic polyurethanes, acrylates or MBS.

13. Polyphenylene oxides and sulfides and mixtures thereof with styrenepolymers or polyamides.

14. Polyurethanes derived from polyethers, polyesters orhydroxyl-terminated polybutadienes on the one hand and aliphatic oraromatic polyisocyanates on the other, as well as precursors thereof.

15. Polyamides and copolyamides derived from diamines and dicarboxylicacids and/or from aminocarboxylic acids or the corresponding lactams,such as polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6,12/12, polyamide 11, polyamide 12, aromatic polyamides obtained bycondensation of m-xylene dianfine and adipic acid; polyamides preparedfrom hexamethylenediamine and isophthalic or/and terephthalic acid andoptionally an elastomer as modifier, for examplepoly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide; and also copolymers of the aforementioned polyamideswith polyolefins, olefin copolymers, ionomers or chemically bonded orgrafted elastomers; or with polyethers, as with polyethylene glycols,polypropylene glycols or polytetramethylene glycols; polyamides orcopolyamides modified with EPDM or ABS; polyamides condensed duringprocessing (RIM polyamide systems).

16. Polyureas, polyimides, polyamide-imides and polybenzimidazoles.

17. Polyesters derived from dicarboxylic acids and diols and/or fromhydroxycarboxylic acids or the corresponding lactones, such aspolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate,poly[2,2,-(4-hydroxyphenyl)propane] terephthalate andpolyhydroxybenzoates as well as block copolyether esters derived fromhydroxyl-terminated polyethers; and also polyester modified withpolycarbonates or MBS.

18. Polycarbonates and polyester carbonates.

19. Polysulfones, polyether sulfones and polyether ketones.

20. Polyethers of digylcidyl compounds, typically diglycidyl ethers anddiols, e.g. of the diglycidyl ether of bisphenol A and bisphenol A.

21. Natural polymers, such as cellulose, rubber, gelatin and chemicallymodified homologous derivatives thereof, such as cellulose acetates,cellulose propionates and cellulose butyrates, or the cellulose etherssuch as methyl cellulose; as well as rosins and their derivatives.

22. Blends of the aforementioned polymers (polyblends), for examplePP/EPDM, polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR,PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPE/HIPS, PPE/PA 66 andcopolymers, PA/HDPE, PA/PP, PA/PPO, PC/poly(epichlorohydrin).

Preferred thermoplastic polymers are polyolefins, polystyrene, polyvinylchloride, polyvinylidene chloride, polyvinylidene fluoride,polyacrylates, polymethacrylates, polyamides, polyesters,polycarbonates, aromatic polysulfones, aromatic polyethers, aromaticpolyether sulfones, polyimides and polyvinyl carbazole.

The thermosetting and structurally crosslinked polymers may be typicallythe following polymers:

1. Crosslinked polymers which are derived from aldehydes on the one handand phenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

2. Drying and non-drying alkyl resins.

3. Unsaturated polyester resins which are derived from copolyesters ofsaturated and unsaturated dicarboxylic acids with polyhydric alcoholsand vinyl compounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

4. Crosslinkable acrylic resins derived from substituted acrylic esterssuch as epoxy acrylates, urethane acrylates or polyester acrylates.

5. Alkyl resins, polyester resins or acrylate resins which arecross-linked with melamine resins, urea resins, polyisocyanates or epoxyresins.

6. Rubber derived from crosslinked polydienes, for example butadiene orisoprene; silicon rubber.

7. Epoxy resins which are derived from polyepoxides, for example frombisglycidyl ethers or from cycloaliphatic diepoxides, and which maycontain a hardener as crosslinking agent or which are crosslinkedthermally using curing accelerators or by irradiation.

Among the crosslinked polymers, crosslinked epoxy resins are preferredwhich, as polyepoxides, are derived preferably from glycidyl compoundswhich contain on average two epoxy groups in the molecule. Particularlysuitable glycidyl compounds are those which contain two glycidyl groups,β-methylglycidyl groups or 2,3-epoxycyelopentyl groups attached to ahetero atom (e.g. sulfur, preferably oxygen or nitrogen), in particularbis(2,3-epoxycyclopentyl) ether; diglycidyl ethers of polyhydricaliphatic alcohols, such as 1,4-butanediol, or polyalkylene glycols,such as polypropylene glycols; diglycidyl ethers of cycloaliphaticpolyols, such as 2,2-bis(4-hydroxycyclohexyl)propane; diglycidyl ethersof polyhydric phenols, such as resorcinol, bis(p-hydroxyphenyl)methane,2,2-bis-(p-hydroxyphenyl)propane (═diomethane),2,2-bis(4'-hydroxy-3'5'-dibromophenyl)propane,1,3-bis(p-hydroxyphenyl)ethane; bis(β-methylglycidyl) ethers of theabove dihydric alcohols or dihydric phenols; diglycidyl esters ofdicarboxylic acids, such as phthalic acid, terephthalic acid, Δ₄-tetrahydrophthalic acid and hexahydrophthalic acid; N,N-diglycidylderivatives of primary amines and amides and heterocyclic nitrogen baseswhich contain two N-atoms, and N,N'-diglycidyl derivatives ofdisecundary diamides and diamines, such as N,N-diglycidylaniline,N,N-diglycidyltoluidine, N,N-diglycidyl-p-aminophenyl methyl ether,N,N'-dimethyl-N,N'-diglycidylbis(p-aminophenyl)methane;N',N"-diglycidyl-N-phenyl-isocyanurate; N,N'-diglycidyl ethyleneurea;N,N'-diglycidyl-5,5-dimethylhydantoin,N,N'-diglycidyl-5-isopropyl-hydantoin,N,N-methylenebis-(N',N'-diglycidyl-5,5-dimethylhydantoin),1,3-bis(N-glycidyl-5,5-dimethylhydantoin)-2-hydroxypropane;N,N'-diglycidyl-5,5-dimethyl-6-isopropyl-5,6-dihydrouracil, triglycidylisocyanurate.

A preferred group of epoxy resins comprises glycidylated novolaks,hydantoins, aminophenols, bisphenols and aromatic dianfines orcycloaliphatic epoxy compounds. Particularly preferred epoxy resins areglycidylated cresol novolaks, bisphenol A and bisphenol F diglycidylether, hydantoin-N,N'-bisglycide, p-aminophenol triglycide,diaminodiphenylmethane tetraglycide, vinylcyclohexene dioxide,3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexanecarboxylate or mixturesthereof.

Further suitable epoxy resins are prereacted adducts of such epoxycompounds with epoxy hardeners, for example an adduct of bisphenol Adiglycidyl ether and bisphenol A, or adducts which have been prereactedwith oligoesters which carry two terminal carboxyl groups and epoxides.

Suitable hardeners for epoxy resins are acid or basic compounds.Illustrative examples of suitable hardeners are: polyhydric phenols(resorcinol, 2,2-bis(4-hydroxyphenyl)propane) or phenol-formaldehyderesins; polybasic carboxylic acids and the anhydrides thereof, such asphthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalicarthydride, 4-methylhexahydrophthalic anhydride,3,6-endomethhylene-tetrahydrophthalic anhydride,4-methyl-3,6-endomethylen-tetrahydrophthalic anhydride (methylnadicanhydride), 3,4,5,6,7,7-hexachloroendomethylene-tetrahydrophthalicanhydride, succinic anhydride, adipic anhydride, trimethyladipicanhydride, sebacic anhydride, maleic anhydride, dodecylsuccinicanhydride, pyromellitic dianhydride, trimellitic anhydride,benzophenonetetracarboxylic dianhydride, or mixtures of such anhydrides.

A preferred group of hardeners comprises novolaks and polycarboxylicanhydrides.

The epoxy resins can also be additionally cured with curing acceleratorsor only with thermal curing catalysts. Exemplary of curing acceleratorsand catalysts are 3-ethyl-4methylimidazole, triamylamrnonium phenolate;mono- or polyphenols (phenol, diomethane, salicylic acid); borontrifluoride and the complexes thereof with organic compounds, such asboron trifluoride ether complexes and boron trifluoride amine complexes(BF₃ /monoethylamine complex); phosphoric acid and triphenylphosphite.

Curing accelerators and catalysts are normally added in an amount of 0.1to 10 % by weight, based on the epoxy resin. Hardeners for epoxy resinsare normally used in equimolar amounts, based on the epoxy groups andfunctional groups of a hardener.

Further additives for enhancing processing properties, the mechanical,electrical and thermal properties, surface properties and lightstability can be blended into the novel formulation. Exemplary of suchadditives are finely particulate fillers, reinforcing fillers,plasticisers, lubricants and mould release agents, adhesion promoters,antistatic agents, antioxidants, heat and light stabilizers, pigmentsand dyes.

In a preferred embodiment of the invention, the novel compositions areshaped to mouldings, films, foils, fibers, or to coatings on at leastone surface of a substrate.

In yet another of its aspects, the invention relates to a process forthe preparation of novel compositions, which comprises (a) blending a CTcomplex of formula I into a thermoplastic polymer, (b) blending a CTcomplex of formula I with at least one component of a thermosetting orstructurally crosslinkable polymer and then polymerizing the blend,together with a further optional component, to a thermosetting orstructurally crosslinked polymer, or (c) dissolving a compound offormula II or a fulvalene derivative of formula III or IIIa, togetherwith a thermoplastic polymer or with at least one component of athermosetting or structurally crosslinkable polymer in an organicsolvent, mixing this solution, together with further optional componentsof a thermosetting or structurally crosslinkable polymer with a solutionof a fulvalene derivative of formula 1/I or IIIa or a compound offormula II, removing the solvent and polymerizing curable mixtures to athermosetting or structurally crosslinked polymer. The process can becombined with a shaping process.

The preparation of the novel compositions can be carried out by methodsknown in plastics technology. In shaping techniques for polymers,typically casting, compression moulding, injection moulding andextrusion, the CT complex itself can be added to a thermoplastic polymeror to at least one component of a thermosetting plastic to form asuspension, or separately to each component (e.g. the epoxy resin andthe hardener) to form a solution or suspension, such that after shapingthe CT complex crystallises and precipitates in the form of needlesduring cooling and the needless form a network in a polymer matrix.

In a particularly preferred embodiment of the invention, the novelcomposition is in the form of a film or foil or a coating on at leastone surface of a substrate. Such embodiments are conveniently preparedby suspending and/or dissolving a thermoplastic polymer or at least onestarting material of a thermosetting polymer or a structurallycrosslinked polymer in an inert solvent together with a CT complex offormula I, or dissolving a thermoplastic polymer or at least onestarting material of a thermosetting polymer or a structurallycrosslinked polymer together with a compound of formula II or afulvalene derivative B, and then mixing the solution or suspension witha solution of the fulvalene derivative B or a compound of formula II,and subsequently applying the mixture by known coating techniques to asubstrate which may be preheated, and thereafter removing the solvent byheating, such that crosslinkable mixtures can then be fully cured.Self-supporting films and foils are obtained by peeling the coating fromthe substrate or by extrusion.

Examples of suitable substrates are glass, metals, plastics, mineral andceramic materials, wood and paper. The substrates may be of any externalshape and are typically mouldings, filaments, fibers, fabrics, bars,pipes, ribbons, sheets, boards, rolls or casings.

Suitable coating techniques are typically brushing, rolling, doctorcoating, casting, spin coating, curtain coating and spraying. Sprayingmethods are especially preferred, as on the one hand very thin anduniform layers with substantially isotropic, very fine-mesh andhomogeneous networks are obtainable from crystal needles of the CTcomplexes and, on the other, the size of the crystal needles and themesh width of the networks can be controlled by the droplet size, evenwhen suspensions are sprayed.

Suitable inert solvents for polymers and starting materials for polymersare typically polar and, preferably, aprotic solvents, which may be usedsingly or in mixtures of at least two solvents. Representative examplesof such solvents are: ethers (dibutyl ether, tetrahydrofuran, dioxane,ethylene glycol monomethyl or dimethyl ether, ethylene glycol monoethylor diethyl ether, diethylene glycol diethyl ether, triethylene glycoldimethyl ether), halogenated hydrocarbons (methylene chloride,chloroform, 1,2-dichloroethane, 1,1,1-trichloroethane,1,1,2,2-tetrachloroethane), carboxylates and lactones (ethyl acetate,methyl propionate, ethyl benzoate, 2-methoxyphenyl acetate,γ-butyrolactone, δ-valerolactone, pivalolactone), carboxamides andlactams (N,N-dimethylformamide, N,N-diethylformamide,N,N-dimethylacetamide, tetramethylurea, hexamethylphosphofic triamide,γ-butyrolactam, ε-caprolactam, N-methylpyrrolidone, N-acetylpyrrolidone,N-methylcaprolactam), sulfoxides (dimethyl sulfoxide), sulfones(dimethyl sulfone, diethyl sulfone, trimethylene sulfone, tetramethylenesulfone), tertiary amines (N-methylpiperidine, N-methylmorpholine)substituted benzenes (benzonitrile, chlorobenzene, o-dichlorobenzene,1,2,4-trichlorobenzene, nitrobenzene, toluene, xylene) and nitriles(acetonitrile, propionitrile). Further suitable solvents arearomatic-aliphatic ethers such as methyl or ethyl phenyl ether as wellas ketones such as acetone, methyl ethyl ketone, methyl propyl ketone,methyl butyl ketone, dipropyl ketone, dibutyl ketone and methyl isobutylketone. Suitable solvents for the compounds of formula II and thefulvalene derivatives B have been mentioned hereinabove.

The coating techniques can conveniently be carried out by dissolving theindividual components separately and combining them just beforeapplication of the chosen technique. However, it is also possible toprepare two solutions of the components, for example of polymer solutionand fulvalene derivative B or of a compound of formula II, and solutionof a compound of formula II or of a fulvalene derivative B together witha polymer, or to combine all the components in one solution. In thislast mentioned case, the CT complexes can crystallise out already priorto coating; but this has virtually no effect on the desired quality ofthe coating.

The solutions are preferably heated, conveniently to 30°-200° C. It isuseful to heat the substrate as well to accelerate the removal of thesolvent, which is normally effected in temperature range from 50° to150° C., preferably 50° to 100° C., until the coating is dry. If it isdesired to detach the coatings to give self-supporting films or sheets,the substrate can be treated with antiblocking agents prior to coating.

An alternative coating method comprises suspending the CT complexes,which are obtained as needle-shaped crystals, in a solution of a polymeror of starting materials for thermosetting polymers, then coating asubstrate and afterwards removing the solvent, and, if appropriate,thereafter effecting a cure to form the thermosetting polymers. It isalso possible to prepare dry powder mixtures from polymer powders orsolid starting materials for thermosetting polymers and the CTcomplexes, and to process these mixtures in coating or electrostaticcoating methods to layers on substrates. Networks of crystal needless ina polymer matrix are also obtained in these alternative methods.

It is also possible to produce pure layers of networks of crystalneedles of the CT complexes on a substrate by applying to a substratesolutions or suspensions of the CT complexes in a solvent and afterwardsevaporating the solvent. Such layers can be electrochemically metallizedto enhance the conductivity, conveniently with Cu, Pt or Pd. It can beuseful to provide such pure layers with a protective coating of apolymer or to coat the pure layers subsequently with a polymer.

The layer thicknesses can vary over a wide range, depending on thechoice of coating method. Spray methods give very thin layers, whereasthicker layers can also be obtained with brushing and casting methods.The layer thicknesses can be typically from 0.01 to 5000 μm, preferablyfrom 0.1 to 1000 μm and, most preferably, from 0.1 to 500 μm.

Depending on the choice of polymer, the novel compositions are opaque ortransparent and have outstanding electrical properties. Thus,surprisingly, the coatings and moundlings have an excellent dischargecapacity which, for heterogeneous materials, is otherwise difficult toachieve or cannot be achieved at all. The compositions are thereforeespecially suitable for use for making antistatically treated mouldedpans for the electrostatic screening of components or for makingantistatically treated mouldings. The high conductivities also permitthe use of the novel compositions as electric conductors, for example aselectrodes for display elements or electronic components as well ascharge carriers in capacitors. The compositions also have excellentmechanical strength and performance properties. The compositions canalso be prepared at comparatively low temperatures and have theadditional advantage of causing no or only insignificant corrosion inmetallic machine pans. Furthermore, they have good stability to theaction of heat and/or moisture.

Further objects of the invention are the use of the novel chargetransfer complexes of formula I as electric conductors; the use of thenovel compositions as antistatically treated moulded pans for theelectronic screening of components or as antistatically treatedmouldings; the use of the novel compositions as electric conductors; theuse of the novel compositions as electrode material; and the use of thenovel compositions in the form of films or foils as charge carriers incapacitors.

The following Examples illustrate the invention in more detail.

A) PREPARATION OF THE CT COMPLEXES Example A1: Preparation of a CTcomplex from tetrahiofulvalene and 5,7,12,14-pentacenetetracyanoimine

A solution warmed to 80° C. of 200 mg (0.460 mmol) of5,7,12,14-tetracenetetracyanoimine in 200 ml of 1,2-dichloroethane isadded to a solution warmed to the same temperature of 94 mg (0.460 mmol)of tetrathiofulvalene in 10 ml of 1,2-dichloroethane. The resultant darkyellow suspension is first cooled to room temperature and then to -5° C.The precipitate is isolated by filtration, washed With CH₂ Cl₂ and thendried under a high vacuum to give dark green crystal needless of thetitle compound in a yield of 197 mg (67 %). The pressed pelletconductivity is 19.0 S/cm. Elemental analysis found (calcd.): C 59.75(60.17); H 2.35 (2.21); N 17.48 (17.54); S 19.80 (20.08). Decompositiontemperature 256° C.

Example A2: Preparation of a CT complex fromtetramethyltetrathiofulvalene and 5,7,12,14-pentacenetetracyanoimine

A solution warmed to 80° C. of 130 mg (0.506 mmol) oftetramethyltetrathiofulvalene in 20 ml of 1,2-dichlorethane is added toa solution warmed to the same temperature of 217 mg (0.500 mmol) of5,7,12,14-pentacenetetracyanoimine in 200 ml of 1,2-dichlorethane. Theresultant dark yellow suspension is first cooled to room temperature andthen to -5° C. The precipitate is isolated by filtration, washed withCH₂ Cl₂ and then dried under a high vacuum to give dark red crystalneedles of the title compound in a yield of 211 mg (61%). The pressedpellet conductivity is 9.0 S/cm. Elemental analysis found (calcd.): C61.83 (61.23); H 3.12 (3.19); N 16.28 (16.13); S 18.05 (18.46).Decomposition temperature 226° C.

Example A3: Preparation of a CT complex frombis(dithioethylene)tetrahiofulvalene and5,7,12,14-pentacenetetracyanoimine

A solution warmed to 100° C. of 57 mg (0.13 mmol) of5,7,12,14-pentacenetetracyanoimine in 30 ml of anisole is added to asolution warmed to the same temperature of 100 mg (0.260 mmol) ofbis(dithioethylene)tetrathiofulvalene in 20 ml of anisole. The resultantred suspension is cooled to room temperature. The precipitate isisolated by filtration, washed with diethyl ether and then dried under ahigh vacuum to give black crystal needles of the title compound in ayield of 90 mg (57 %). The pressed pellet conductivity is 1.3×10⁻² S/cm.Elemental analysis found (calcd.): C 46.45 (45.90); H 2.50 (2.18); N9.30 (9.31); S 42.43 (42.62).

Example A4: Preparation of a CT complex from tetraselenofulvalene and5,7,12,14-pentacenetetracyanoimine

A solution warmed to 100° C. of 111 mg (0.260 mmol) of5,7,12,14-pentacenetetracyanoimine in 30 ml of anisole is added to asolution warmed to the same temperature of 100 mg (0.260 mmol) oftetraselenofulvalene in 20 ml of anisole. The resultant red solution iscooled to -5° C. The precipitate is isolated by filtration, washed withdiethyl ether and then dried under a high vacuum to give 90 mg (57 %)dark red crystal needles of the title compound with a pressed pelletconductivity of 4.8 S/cm. Elemental analysis found (calcd.): C 46.90(46.51); H 1.78 (1.71); N 13.56 (13.56); Se 37.80 (38.22).

B) USE EXAMPLES Example B1:

A solution warmed to 70° C. of 4 mg of5,7,12,14-pentacenetetracyanoimine in 3 ml of 1,2-dichloroethane isadded to a solution warmed to the same temperature of mg ofpolycarbonate and 1.5 mg of tetrathiofulvalene in 3 ml of1,2-dichloroethane. Aliquots of the mixture are poured on to a glassplate and the solvent is evaporated at different temperatures. Theconductivity of the foils so obtained is measured.

    ______________________________________                                        Evaporation temperature (°C.)                                                             Conductivity (S/cm)                                        ______________________________________                                        40                 0.03                                                       45                 0.14                                                       50                 0.03                                                       ______________________________________                                    

What is claimed is:
 1. A composition comprising a) a thermosetting,thermoplastic or structurally crosslinked polymer and b) a chargetransfer complex of formula I in the form of a network of crystalneedles in the polymer matrix

    [A].sup.⊖ ·B.sup.⊕

wherein A is a compound of formula II or a mixture of compounds offormula II ##STR8## wherein the R substituents are identical and are Hor C₁ -C₄ -alkyl, or the adjacent R substituents, taken together, are--(CH₂)₃ --, or --(CH₂)₄ --; R₁ is H or C₁ -C₄ alkyl; and X₁ is ═N--CN,and X₂, X₃ and X₄ are ═O or ═N--CN, and B is a compound of formula IIIor IIIa ##STR9## wherein R₂, R₃, R₄ and R₅ are each independently of oneanother H, linear or branched C₁ -C₁₈ alkyl--(Z₁)_(n) --,phenyl--(Z₁)_(n) --, or benzyl--(Z₁)_(n) --which are unsubstituted orsubstituted by C₁ -C₄ alkyl, C₁ -C₄ alkoxy or C₁ -C₄ alkylthio, or R₂and R₃ as well as R₄ and R₅ are together, each independently of theother trimethylene, tetramethylene, --Z₂ --(CH₂)--Z₂ --, --Z₂ --(CH₂)₂--Z₂ --, --Z₁ --CH═CH--Z₁ -- or --CH═CH--CH═CH--, each unsubstituted orsubstituted by C₁ -C₄ alkyl, C₁ -C₄ alkoxy or C₁ -C₄ alkylthio, n is 0is 1, Y₁ and Y₂ are each independently of the other --S-- or --Se--, Z₁is --S-- or --Se--, Z₂ is --O--, --S-- or --Se--, Z is --S--, -- Se-- orNR₇, and R₇ is H, C₁ -C₆ alkyl, phenyl or benzyl, and R₆ is H, C₁ -C₄alkyl, phenyl or benzyl.
 2. A composition according to claim 1, whereinthe compounds of formulae III and IIIa have a reduction potential ofless than or equal to 0.42 V, based on the standard calomel electrode.3. A composition according to claim 1, wherein R in formula II is C₁ -C₄alkyl and R₁ is H.
 4. A composition according to claim 1, wherein R1 informula II is C₁ -C₄ alkyl and R is H.
 5. A composition according toclaim 1, wherein R and R₁ in formula II are H, methyl or ethyl.
 6. Acomposition according to claim 1, wherein in formula II X₁ and X₄ are═N--CN and X₂ and X₃ are ═O or ═N--CN, or X₂ and X₃ are ═N--CN and X₁and X₄ are ═O or ═N--CN.
 7. A composition according to claim 1, whereinX₁, X₂, X₃ and X₄ in formula II are ═N--CN.
 8. A composition accordingto claim 1, wherein R₂ and R₃ as well as R₄ and R₅ in formula III areidentical.
 9. A composition according to claim 1, wherein Y₁ and Y₂ informula III and IIIa are each --S--.
 10. A composition according toclaim 1, wherein R₂ to R₅ in formula III defined as alkyl--(Z₁)_(n)--are C₁ -C₁₂ alkyl--(Z₁)_(n) --, wherein Z₁ and n are as defined inclaim
 1. 11. A composition according to claim 1, wherein alkyl--(Z₁)_(n)--is methyl, ethyl, n- and isopropyl, n-, iso- and tert-butyl,methylthio, methylseleno, ethylthio and ethylseleno.
 12. A compositionaccording to claim 1, wherein R₆ in formula IIIa is H or C₁ -C₄ alkyl.13. A composition according to claim 1, wherein Z₁ is --S--and Z₂ is--S--or --O--.
 14. A composition according to claim 1, wherein the CTcomplex of formula I is one in which, in formula II, R is H, methyl orethyl, R₁ is H or methyl and X₁ to X₄ are ═N--CN, and, in formulae IIIand IIIa, R₂ and R₃ as well as R₄ and R₅ or R₂ to R₅ are identical andare H, linear or branched C₁ -C₈ alkyl--(Z₁)_(n) --, unsubstituted or C₁-C₄ alkyl-substituted phenyl--(Z₁)_(n) --or benzyl--(Z₁)_(n) --, or R₂and R₃ as well as R₄ and R₅ are together, each independently of theother, unsubstituted or C₁ -C₄ alkyl-substituted trimethylene,tetramethylene, --Z₂ --(CH₂)--Z₂ --, --Z₂ --(CH₂)₂ --Z₂ --, --Z₁--CH═CH--Z₁ --or --CH═CH--CH═CH--, n is 0 or 1, Y₁ and Y₂ are --S--, Z₁is --S--, Z₂ is --O--or --S--, Z is --S--or NR₇, and R₇ is H or C₁ -C₄alkyl, and R₆ is H or C₁ -C₄ alkyl.
 15. A composition according to claim14, wherein the CT complex of formula I is one in which, in formula II,R and R₁ are H, X₁ to X₄ are ═N--CN, and in formulae III and IIIa R₂ toR₅ are identical and are H, or are linear or branched C₁ -C₄alkyl--(Z₁)_(n) --, or R₂ and R₃ as well as R₄ and R₅ are each togethertrimethylene, tetramethylene, --Z₂ --(CH₂)--Z₂ --, --Z₂ --(CH₂)₂ --Z₂--, --Z₁ --CH═CH--Z₁ --or --CH═CH--CH═CH--, n is 0 or 1, Y₁ and Y₂ are--S--, Z₁ is --S--, Z₂ is --O--or --S--, Z is --S--or NR₇, and R₇ is Hor C₁ -C₄ alkyl, and R₆ is H or C₁ -C₄ alkyl.
 16. A compositionaccording to claim 1, wherein the CT complexes of formula I are thoseion which A is 5,7,12,14-pentacenetetracyanoimine and B is a compound offormula IIIb ##STR10## wherein Y₁ and Y₂ are each --S--, and R₂, R₃, R₄and R₅ are each independently of one another H, C₁ -C₄ alkyl or C₁ -C₄alkylthio or R₂ and R₃ as well as R₄ and R₅ together are --S--CH₂ CH₂--S--.
 17. A composition according to claim 16, wherein the CT complexesof formula I are those in which A in formula I is5,7,12,14-pentacenetetracyanoimine, and B is selected from the groupconsisting of tetrathiofulvalene, tetramethyltetrathiofulvalene,tetramethyltetrathiofulvalene, dimethyldiethyltetrathiofulvalene,tetra-n-propyltetrathiofulvalene, tetra-n-butyltetrathiofulvalene,tetra(methylthio)tetrathiofulvalene, tetra(ethylthio)tetrathiofulvalene,tetra(n-propylthio)tetrathiofulvalene,tetra(n-butylthio)tetrathiofulvalene,dimethyldimethylthiotetrathiofulvalene,diethyldimethylthiotetrathiofulvalene,diethylthiodimethylthiotetrathiofulvalene and tetraselenofulvalene. 18.A composition according to claim 17, which contains the charge transfercomplex in an amount of 0.01 to 30 % by weight, based on the weight ofsaid composition.
 19. A composition according to claim 17, whichcontains the charge transfer complex in an amount of 0.01 to 10 % byweight.
 20. A composition according to claim 1, wherein thethermoplastic polymer is selected from the group consisting ofpolyolefins, polystyrene, polyvinyl chloride, polyvinylidene chloride,polyvinylidene fluoride, polyacrylates, polymethacrylates, polyamides,polyesters, polycarbonates, aromatic polysulfones, aromatic polyethers,aromatic polyether sulfones, polyimides and polyvinyl carbazole.
 21. Acomposition according to claim 1, wherein the thermosetting polymer isan epoxy resin.
 22. A composition according to claim 1 which is shapedto mouldings, films, toils, fibers or a coating on at least one surfaceof a substrate.
 23. A composition according to claim 22, wherein thelayer thickness of the coating is from 0.01 to 5000 μm.
 24. Acomposition according to claim 23, wherein the layer thickness of thecoating is from 0.1 to 1000 μm.
 25. A composition according to claim 1,wherein R and R₁ are methyl or ethyl.
 26. A composition according toclaim 1, wherein R and R₁ are H.
 27. A composition according to claim 1,wherein R₂, R₃, R₄ and R₅ are identical.